Detergent containing glucanase

ABSTRACT

A detergent composition comprising a β-glucanase is presented. The β-glucanase improves the cleaning performance of the detergent, especially with respect to polysaccharide soils.

This application is filed under 35 U.S.C. 371 and based onPCT/EP98/04578, filed Jul. 21, 1998.

BACKGROUND OF THE INVENTION

1. Field of the Invention

This invention relates to laundry detergents which contain β-glucanaseto improve their cleaning performance.

2. Discussion of Related Art

Enzymes, especially proteases, lipases and cellulases, but alsoamylases, are widely used in laundry detergents, washing aids anddishwashing detergents. Proteases, lipases or amylases are primarilyused to remove protein, fatty and starch soils. By contrast, cellulasesoccupy a special position because they are not used to remove specialsoils, but instead have been known for some time as softening agents forcotton fabrics by virtue of their ability to degrade cellulose. A sideeffect of the degradation of cellulose fibrils by cellulases is thedeepening of the optical color impression, the so-called colorfreshening effect, which is obtained in the treatment of colored cottonfabrics with cellulases when the undyed fibrils resulting from fiberdamage from within the fibers are removed.

In connection with polysaccharide soils, there is the problem thatnaturally occurring polysaccharides, for example as present in foods, donot normally consist solely of starch, but also contain othersaccharides or differently linked saccharides. Whereas α-amylasesintended for use in laundry detergents are generally very suitable forhydrolyzing the starch component of polysaccharide soils intowater-soluble oligosaccharides, their soil removal capacity can beunsatisfactory when the soils in question are soils of otherpolysaccharides or when these other polysaccharides make up relativelylarge parts of the polysaccharide soils.

The problem addressed by the present invention was to remedy thissituation and to provide a detergent which would have an improvedcleaning performance with respect to polysaccharide soils.

DESCRIPTION OF THE INVENTION

The present invention, which is intended to solve the problem statedabove, relates to a detergent suitable for use in the washing of laundrywhich contains a β-glucanase in addition to typical ingredientscompatible with this enzyme.

β-Glucanases in the context of the present invention are enzymes fromthe class of endo-1,3-1,4-β-D-glucan-4-glucanohydrolases (EC 3.2.1.73;lichenases). β-Glucanases in the context of the invention also includeendo-1,3-β-D-glucosidases (EC 3.2.1.39; laminarinases). β-Glucanasescleave mixed glucans, which are linked alternately by 1,3- and1,4-β-glucoside bonds, into oligosaccharides. Polymeric mixed glucanssuch as these are present in varying amounts in virtually all cerealproducts. Hitherto, enzymes capable of cleaving them have been usedabove all in the food, beverage and animal feed industry, in the textileindustry and in the processing of starch (R. Borriss,“β-Glucan-spaltende Enzyme”, in H. Ruttloff: “Industrielle Enzyme”,Chapter 11.5, Behr's Verlag, Hamburg, 1994).

β-Glucanases suitable for use in accordance with the invention areobtainable from microorganisms, for example Achromobacter lunatus,Athrobacter luteus, Aspergillus aculeatus, Aspergillus niger, Bacillussubtilis, Disporotrichum dimorphosporum, Humicola insolens, Penicilliumemersonii, Penicillium funiculosum or Trichoderna reesei. A commercialproduct is marketed, for example, under the name of Cereflo®(manufacturer: Novo Nordisk A/S). Preferred β-Glucanases include anenzyme obtainable from Bacillus alkalophilus (DSM 9956) which is thesubject of German patent application DE 197 32 751.

β-Glucanase is preferably incorporated in compositions according to theinvention in such quantities that they have glucanolytic activities of0.05 U/g to 1 U/g and more particularly in the range from 0.06 U/g to0.25 U/g. The determination of the glucanolytic activity is based onmodifications of the process described by M. Lever in Anal. Biochem. 47(1972), 273-279 and Anal Biochem. 81 (1977), 21-27. A 0.5% by weightsolution of β-glucan (Sigma No. G6513) in 50 mM glycine buffer (pH 9.0)is used for this purpose. 250 μl of this solution are added to 250 μl ofa solution containing the agent to be tested for glucanolytic activityand incubated for 30 minutes at 40° C. 1.5 ml of a 1% by weight solutionof p-hydroxybenzoic acid hydrazide (PAHBAH) in 0.5 M NaOH, whichcontains 1 mM bismuth nitrate and 1 mM potassium sodium tartrate, arethen added, after which the solution is heated for 10 minutes to 70° C.After cooling (2 minutes/0° C.), the absorption at 410 nm is determinedagainst a blank value at room temperature (for example with a Uvikon®930 photometer) using a glucose calibration curve. The blank value is asolution which is prepared in the same way as the measuring solutionexcept that the glucan solution is added after the PAHBAH solution. 1 Ucorresponds to the quantity of enzyme which produces 1 μmole of glucoseper minute under these conditions.

The present invention also relates to the use of β-glucanase forremoving polysaccharide soils from textiles and to a process forremoving polysaccharide soils from textiles by using β-glucanase. Forthe use according to the invention and for the process according to theinvention, the β-glucanase may be applied to polysaccharide-soiledtextiles either on its own or as part of a laundry pretreatmentcomposition in the course of a pretreatment step preceding the washingprocess. However, the β-glucanase is preferably used as part of anaqueous cleaning solution which may additionally contain typicalingredients of wash liquors. Glucanolytic activities of 0.2 U/l to 4 U/land, more particularly, 0.25 U/l to 1 U/l in the aqueous cleaningsolution are preferred. In machine washing processes, for example in theroutine washing of domestic laundry in washing machines, theglucanolytic activities mentioned do not have to be maintained over theentire washing cycle to achieve the required washing result providing itis guaranteed that a glucanolytic activity in the range mentionedprevails for at least a short time, for example for about 5 to 20minutes.

β-Glucanase may be adsorbed onto supports and/or encapsulated inshell-forming substances to protect it against premature inactivation,particularly where it is used in particulate detergents as described,for example, in European patent EP 0 564 476 or in International patentapplications WO 94/23005 for other enzymes.

In the course of the development work on which the present invention isbased, it was surprisingly found that, if desired, amylase need not beused at all with no significant loss of cleaning performance againstpolysaccharide soils consisting at least partly of starch.

Since the washing performance of proteolytic and β-glucanolytic enzymesis unexpectedly increased when they are used in combination, a laundrydetergent according to the invention preferably contains at least oneprotease in addition to β-glucanase. A detergent according to theinvention is distinguished in particular by a proteolytic activity ofabout 100 PU/g to about 7500 PU/g and, more particularly, in the rangefrom 500 PU/g to 5000 PU/g. The protease activity is determined by thestandardized method described in the following (cf. Tenside 7 (1970),125): a solution containing 12 g/l casein and 30 mM sodiumtripolyphosphate in water with a hardness of 15°dH (containing 0.058% byweight CaCl₂.2H₂O, 0.028% by weight MgCl₂.6H₂O and 0.042% by weightNaHCO₃) is heated to 70° C. and the pH is adjusted to 8.5 by addition of0.1 N NaOH at 50° C. 200 ml of a solution of the agent to be tested forproteolytic activity in 2% by weight sodium tripolyphosphate buffersolution (pH 8.5) are added to 600 ml of the substrate solution. Thereaction mixture is incubated for 15 minutes at 50° C. The reaction isthen stopped by addition of 500 ml of TCA solution (0.44 Mtrichloroacetic acid and 0.22 M sodium acetate in 3% by volume aceticacid) and cooling (ice bath at 0° C., 15 minutes). The TCA-insolubleprotein is removed by centrifuging and 900 ml of the supernatant arediluted with 300 ml 2 N NaOH. The absorption of this solution at 290 nmis determined with an absorption spectrometer, the zero absorption valuehaving to be determined by measuring a centrifuged solution prepared bymixing 600 ml of the above-mentioned TCA solution with 600 ml of theabove-mentioned substrate solution and then adding the enzyme solution.The proteolytic activity of a solution which produces an absorption of0.500 OD under the described measuring conditions is defined as 10 PU(protease units) per ml. The proteases preferably used in compositionsaccording to the invention include the enzymes known from Internationalpatent applications WO 91/02792, WO 92/21760 and WO 95/23221.

Besides the β-glucanase used in accordance with the invention, thedetergents according to the invention—which may be present as, inparticular, powder-form solids, as post-compacted particles or ashomogeneous solutions or suspensions—may in principle contain any knowningredients typically encountered in detergents. More particularly, thedetergents according to the invention may contain builders, surfactants,bleaching agents based on organic and/or inorganic peroxygen compounds,bleach activators, water-miscible organic solvents, additional enzymes,sequestering agents, electrolytes, pH regulators and/or otherauxiliaries, such as optical brighteners, redeposition inhibitors, dyetransfer inhibitors, foam regulators, dyes and perfumes.

The detergents according to the invention may contain one or moresurfactants, more particularly anionic surfactants, nonionic surfactantsand mixtures thereof. Suitable nonionic surfactants are, in particular,alkyl glycosides and ethoxylation and/or propoxylation products of alkylglycosides or linear or branched alcohols containing 12 to 18 carbonatoms in the alkyl moiety and 3 to 20 and preferably 4 to 10 alkyl ethergroups. Corresponding ethoxylation and/or propoxylation products ofN-alkylamines, vicinal diols, fatty acid esters and fatty acid amides,which correspond to the long-chain alcohol derivatives mentioned inregard to the alkyl moiety, and of alkyl phenols containing 5 to 12carbon atoms in the alkyl group are also suitable.

Suitable anionic surfactants are, in particular, soaps and those whichcontain sulfate or sulfonate groups with, preferably, alkali metal ionsas cations. Suitable soaps are preferably the alkali metal salts ofsaturated or unsaturated fatty acids containing 12 to 18 carbon atoms.Fatty acids such as these may also be used in non-completely neutralizedform. Suitable surfactants of the sulfate type include the salts ofsulfuric acid semiesters of fatty alcohols containing 12 to 18 carbonatoms and sulfation products of the nonionic surfactants mentioned witha low degree of ethoxylation. Suitable surfactants of the sulfonate typeinclude linear alkyl benzenesulfonates containing 9 to 14 carbon atomsin the alkyl moiety, alkanesulfonates containing 12 to 18 carbon atomsand olefin sulfonates containing 12 to 18 carbon atoms, which are formedin the reaction of corresponding monoolefins with sulfur trioxide, andα-sulfofatty acid esters which are formed in the sulfonation of fattyacid methyl or ethyl esters.

Surfactants such as these are present in the detergents according to theinvention in quantities of, preferably, 5% by weight to 50% by weightand, more preferably, 8% by weight to 30% by weight.

A detergent according to the invention preferably contains at least onewater-soluble and/or water-insoluble organic and/or inorganic builder.The water-soluble organic builders include polycarboxylic acids, moreparticularly citric acid and sugar acids, monomeric and polymericaminopolycarboxylic acids, more particularly methyl glycine diaceticacid, nitrilotriacetic acid and ethylenediamine tetraacetic acid, andpolyaspartic acid, polyphosphonic acids, more particularlyaminotris-(methylenephosphonic acid),ethylenediamine-tetrakis-(methylenephosphonic acid) and1-hydroxyethane-1,1-diphosphonic acid, polymeric hydroxy compounds, suchas dextrin, and polymeric (poly)carboxylic acids, more particularly thepolycarboxylates obtainable by oxidation of polysaccharides or dextrinsaccording to International patent application WO 93/16110 orInternational patent application WO 92/18542 or European patent EP 0 232202, polymeric acrylic acids, methacrylic acids, maleic acids andcopolymers thereof which may also contain small amounts of polymerizablesubstances with no carboxylic acid functionality in copolymerized form.The relative molecular weight of the homopolymers of unsaturatedcarboxylic acids is generally between 5,000 and 200,000 and that of thecopolymers between 2,000 and 200,000 and preferably between 50,000 and120,000, based on free acid. A particularly preferred acrylicacid/maleic acid copolymer has a relative molecular weight of 50,000 to100,000. Suitable but less preferred compounds of this class arecopolymers of acrylic acid or methacrylic acid with vinyl ethers, suchas vinyl methyl ethers, vinyl esters, ethylene, propylene and styrene,in which the acid makes up at least 50% by weight. Other suitablewater-soluble organic builders are terpolymers which contain twounsaturated acids and/or salts thereof as monomers and vinyl alcoholand/or an esterified vinyl alcohol or a carbohydrate as the thirdmonomer. The first acidic monomer or its salt is derived from amonoethylenically unsaturated C₃₋₈ carboxylic acid and preferably from aC₃₋₄ monocarboxylic acid, more particularly from (meth)acrylic acid. Thesecond acidic monomer or its salt may be a derivative of a C₄₋₈dicarboxylic acid, maleic acid being particularly preferred, and/or aderivative of an allylsulfonic acid substituted in the 2-position by analkyl or aryl group. Polymers such as these may be produced by theprocesses described in German patent DE 42 21 381 and German patentapplication DE 43 00 772 and generally have a relative molecular weightof 1,000 to 200,000. Other preferred copolymers are those which aredescribed in German patent applications DE 43 03 320 and DE 44 17 734and which preferably contain acrolein and acrylic acid/acrylic acidsalts or vinyl acetate as monomers. The organic builders may be used inthe form of aqueous solutions, preferably in the form of 30 to 50% byweight aqueous solutions, especially for the production of liquiddetergents. All the acids mentioned are generally used in the form oftheir water-soluble salts, more particularly their alkali metal salts.

If desired, organic builders of the type in question may be present inquantities of up to 40% by weight, preferably in quantities of up to 25%by weight and more preferably in quantities of 1% by weight to 8% byweight. Quantities near the upper limit mentioned are preferably used inpaste-form or liquid—more particularly water-containing—detergentsaccording to the invention.

Suitable water-soluble inorganic builders are, in particular, alkalimetal silicates and polymeric alkali metal phosphates which may bepresent in the form of their alkaline, neutral or acidic sodium orpotassium salts, Examples include tetrasodium diphosphate, disodiumdihydrogen diphosphate, pentasodium triphosphate, so-called sodiumhexametaphosphate, and the corresponding potassium salts or mixtures ofsodium and potassium salts. Suitable water-insoluble, water-dispersibleinorganic builders are, in particular, crystalline or amorphous alkalimetal alumosilicates which are used in quantities of up to 50% byweight, preferably in quantities of not more than 40% by weight and—inliquid detergents—more particularly in quantities of 1% by weight to 5%by weight. Of these, crystalline sodium alumosilicates in detergentquality, more particularly zeolite A, P and optionally X, are preferred.Quantities near the upper limit mentioned are preferably used in solidparticulate detergents. Suitable alumosilicates above all contain noparticles larger than 30 μm in size, at least 80% by weight consistingof particles below 10 μm in size. The calcium binding capacity, whichmay be measured in accordance with German patent DE 24 12 837, isgenerally in the range from 100 to 200 mg CaO per gram.

Suitable substitutes or partial substitutes for the alumosilicatementioned are crystalline alkali metal silicates which may be present ontheir own or in admixture with amorphous silicates. The alkali metalsilicates suitable as builders in the detergents according to theinvention preferably have a molar ratio of alkali metal oxide to SiO₂below 1:0.95 and, more particularly, between 1:1.1 and 1:12 and may bepresent in amorphous or crystalline form. Preferred alkali metalsilicates are the sodium silicates, more particularly the amorphoussodium silicates, with a molar Na₂O:SiO₂ ratio of 1:2 to 1:2.8. Thosewith a molar Na₂O:SiO₂ ratio of 1:1.9 to 1:2.8 may be produced by theprocess according to European patent application EP 0 425 427. Preferredcrystalline silicates, which may be present on their own or in the formof a mixture with amorphous silicates, are crystalline layer silicateswith the general formula Na₂Si_(x)O_(2x+1).yH₂O where x—the so-calledmodulus—is a number of 1.9 to 4 and y is a number of 0 to 20, preferredvalues for x being 2, 3 or 4. Crystalline layer silicates which fallwithin this general formula are described, for example, in Europeanpatent application EP 0 164 514. Preferred crystalline layer silicatesare those in which x in the general formula shown above assumes thevalue 2 or 3. More particularly, both β- and δ-sodium disilicates(Na₂Si₂O₅.yH₂O) are preferred, β-sodium disilicate being obtainable, forexample, by the process described in International patent application WO91/08171. δ-Sodium silicates with a modulus of 1.9 to 3.2 may beproduced in accordance with Japanese patent applications JP 04/238 809and JP 04/260 610. Substantially water-free crystalline alkali metalsilicates with the above general formula, where x is a number of 1.9 to2.1, produced from amorphous alkali metal silicates as described inEuropean patent applications EP 0 548 599, EP 0 502 325 and EP 0 452 428may also be used in detergents according to the invention. Anotherpreferred embodiment of detergents according to the invention ischaracterized by the use of a crystalline sodium layer silicate with amodulus of 2 to 3 which may be produced from sand and soda by theprocess according to European patent application EP 0 436 835.Crystalline sodium silicates with a modulus of 1.9 to 3.5 obtainable bythe processes according to European patents EP 0 164 552 and/or EP 0 293753 are used in another preferred embodiment of detergents according tothe invention. Another preferred embodiment of detergents according tothe invention is characterized by the use of the granular compound ofalkali metal silicate and alkali metal carbonate which is described, forexample, in International patent application WO 95/22592 or which iscommercially obtainable, for example, as Nabion® 15. If alkali metalalumosilicate, especially zeolite, is also present as an additionalbuilder, the ratio by weight of alumosilicate to silicate, expressed aswater-free active substances, is preferably from 1:10 to 10:1. Indetergents containing both amorphous and crystalline alkali metalsilicates, the ratio by weight of amorphous alkali metal silicate tocrystalline alkali metal silicate is preferably 1:1 to 2:1 and, moreparticularly, 1:1 to 2:1.

Builders are present in the detergents according to the invention inquantities of preferably up to 60% by weight and, more preferably, 5% byweight to 40% by weight.

Suitable peroxygen compounds are, in particular, organic peracids orperacidic salts of organic acids, such as phthalimidopercaproic acid,perbenzoic acid or salts of diperdodecane diacid, hydrogen peroxide andinorganic salts which release hydrogen peroxide under the washingconditions, such as perborate, percarbonate and/or persilicate. Hydrogenperoxide can also be produced by an enzyme system, i.e. an oxidase andits substrate. If solid peroxygen compounds are to be used, they may beused in the form of powders or granules which may also be coated inknown manner. In a particularly preferred embodiment, alkali metalpercarbonate, alkali metal perborate monohydrate, alkali metal perboratetetrahydrate or hydrogen peroxide is used in the form of an aqueoussolution containing 3% by weight to 10% by weight of hydrogen peroxide.If a detergent according to the invention contains peroxygen compounds,the peroxygen compounds are present in quantities of preferably up to50% by weight and, more preferably, 5% by weight to 30% by weight. Theaddition of small quantities of known bleach stabilizers, for examplephosphonates, borates or metaborates and metasilicates and magnesiumsalts, such as magnesium sulfate, can be useful.

The bleach activators may be compounds which form aliphaticperoxocarboxylic acids containing preferably 1 to 10 carbon atoms andmore preferably 2 to 4 carbon atoms and/or optionally substitutedperbenzoic acid under perhydrolysis conditions. Substances bearing O-and/or N-acyl groups with the number of carbon atoms mentioned and/oroptionally substituted benzoyl groups are suitable. Preferred bleachactivators are polyacylated alkylenediamines, more particularlytetraacetyl ethylenediamine (TAED), acylated triazine derivatives, moreparticularly 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),acylated glycolurils, more particularly tetraacetyl glycoluril (TAGU),N-acylimides, more particularly N-nonanoyl succinimide (NOSI), acylatedphenol sulfonates, more particularly n-nonanoyl orisononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides,more particularly phthalic anhydride, acylated polyhydric alcohols, moreparticularly triacetin, ethylene glycol diacetate,2,5-diacetoxy-2,5-dihydrofuran and the enol esters known from Germanpatent applications DE 196 16 693 and DE 196 16 767, acetylated sorbitoland mannitol and the mixtures thereof (SORMAN) described in Europeanpatent application EP 0 525 239, acylated sugar derivatives, moreparticularly pentaacetyl glucose (PAG), pentaacetyl fructose,tetraacetyl xylose and octaacetyl lactose, and acetylated, optionallyN-alkylated glucamine and gluconolactone, and/or N-acylated lactams, forexample N-benzoyl caprolactam, which are known from International patentapplications WO-A-94/27970, WO-A-94/28102, WO-A-94/28103, WO-A-95/00626,WO-A-95/14759 and WO-A-95/17498. The substituted hydrophilic acylacetals known from German patent application DE 196 16 769 and the acyllactams described in German patent application DE 196 16 770 and inInternational patent application WO 95/14075 are also preferably used.The combinations of conventional bleach activators known from Germanpatent application DE 44 43 177 may also be used. Bleach activators suchas these are present in the usual quantities, preferably in quantitiesof 1% by weight to 10% by weight and more preferably in quantities of 2%by weight to 8% by weight, based on the detergent as a whole.

In addition to or instead of the conventional bleach activatorsmentioned above, the sulfonimines known from European patents EP 0 446982 and EP 0 453 003 and/or bleach-boosting transition metal salts ortransition metal complexes may also be present as so-called bleachcatalysts. Suitable transition metal compounds include, in particular,the manganese-, iron-, cobalt-, ruthenium- or molybdenum-salen complexesknown from German patent application DE 195 29 905 and the N-analogcompounds thereof known from German patent application DE 196 20 267,the manganese-, iron-, cobalt-, ruthenium- or molybdenum-carbonylcomplexes known from German patent application DE 195 36 082, themanganese, iron, cobalt, ruthenium, molybdenum, titanium, vanadium andcopper complexes with nitrogen-containing tripod ligands described inGerman patent application DE 196 05 688, the cobalt-, iron-, copper- andruthenium-ammine complexes known from German patent application DE 19620 411, the manganese, copper and cobalt complexes described in Germanpatent application DE 44 16 438, the cobalt complexes described inEuropean patent application EP 0 272 030, the manganese complexes knownfrom European patent application EP 0 693 550, the manganese, iron,cobalt and copper complexes known from European patent EP 0 392 592, thecobalt complexes known from International patent applications WO96/23859, WO 96/23860 and 96/23861 and/or the manganese complexesdescribed in European patent EP 0 443 651 or in European patentapplications EP 0 458 397, EP 0 458 398, EP 0 549 271, EP 0 549 272, EP0 544 490 and EP 0 544 519. Combinations of bleach activators andtransition metal bleach catalysts are known, for example, from Germanpatent application DE 196 13 103 and from international patentapplication WO 95/27775. Bleach-boosting transition metal complexes,more particularly with the central atoms Mn, Fe, Co. Cu, Mo. V, Tiand/or Ru, are used in typical quantities, preferably in a quantity ofup to 1% by weight, more preferably in a quantity of 0.0025% by weightto 0.25% by weight and most preferably in a quantity of 0.01% by weightto 0.1% by weight, based on the detergent as a whole.

Enzymes suitable for use in the detergents besides the β-glucanasecrucial to the invention and the oxidase mentioned above are those fromthe class of proteases, lipases, cutinases, amylases, pullulanases,cellulases, hemicellulases, xylanases and peroxidases and mixturesthereof, for example proteases, such as subtilisin BPN′, Properase®,BLAP®, Optimase®, Opticlean®, Maxatase®, Maxacal®, Maxapem®, Alcalase®,Esperase®, Savinase®, Durazym®, Everlase® and/or Purafect® G or OxP;amylases, such as BAN®, Termamyl®, Amylase-LT®, Maxamyl®, Duramyl®and/or Purafect®OxAm; lipases, such as Lipolase®, Lipomax®, Lumafast®and/or Lipozym®; cellulases, such as KAC®, Celluzyme®, Carezyme®, and/orthe enzymes known from International patent applications WO 96/34108 andWO 97/13862. Enzymes obtained from fungi or bacteria, such as Bacillussubtilis, Bacillus licheniformis, Streptomyces griseus, Humicolalanuginosa, Humicola insolens, Pseudomonas peudoalcaligenes orPseudomonas cepacia are particularly suitable. The additional enzymesoptionally used may also be adsorbed to supports and/or embedded inshell-forming materials for protection against premature inactivation,for example as described in European patent 0 564 476 or inInternational patent application WO 94/23005. They are present in thedetergents according to the invention in quantities of preferably up to10% by weight and, more preferably, from 0.2% by weight to 2% by weight,enzymes stabilized against oxidative degradation, as known for examplefrom International patent applications WO 94/02597, WO 94/02618, WO94/18314, WO 94/23053 or WO 95107350, being particularly preferred. Inone particularly preferred embodiment of the invention, the detergentmay be amylase-free or contains at least minimal amounts of amylasebecause the use of β-glucanase generally enables even amylolyticallyremovable soils on textiles to be removed without any significant lossof performance

The organic solvents suitable for use in the detergents according to theinvention, particularly where they are present in liquid or paste-likeform, include C₁₋₄ alcohols, more especially methanol, ethanol,isopropanol and tert. butanol, C₂₋₄ diols, more especially ethyleneglycol and propylene glycol, and mixtures thereof and ethers derivedfrom the classes of compound mentioned. Water-miscible solvents such asthese are present in the detergents according to the invention inquantities of preferably not more than 30% by weight and, morepreferably, between 6% by weight and 20% by weight.

To establish a desired pH value which is not spontaneously adjusted bythe mixture of the other components, the detergents according to theinvention may contain system-compatible and environmentally compatibleacids, more particularly citric acid, acetic acid, tartaric acid, malicacid, lactic acid, glycolic acid, succinic acid, glutaric acid and/oradipic acid and also mineral acids, more especially sulfuric acid, orbases, more especially ammonium or alkali metal hydroxides. pHregulators such as these are present in the detergents according to theinvention in quantities of preferably not more than 20% by weight and,more preferably, between 1.2% by weight and 17% by weight.

The dye transfer inhibitors suitable for use in detergents according tothe invention, more particularly laundry detergents, include inparticular polyvinyl pyrrolidones, polyvinyl imidazoles, polymerN-oxides, such as poly-(vinlylpyridine-N-oxide) and vinylpyrrolidone/vinyl imidazole copolymers.

The function of redeposition inhibitors is to keep the soil detachedfrom the hard surfaces and particularly from the textile fiberssuspended in the wash liquor. Suitable redeposition inhibitors arewater-soluble, generally organic colloids, for example starch, glue,gelatine, salts of ether carboxylic acids or ether sulfonic acids ofstarch or cellulose or salts of acidic sulfuric acid esters of celluloseor starch. Water-soluble polyamides containing acidic groups are alsosuitable for this purpose. Other starch derivatives than those mentionedabove, for example aldehyde starches, may also be used. Celluloseethers, such as carboxymethyl cellulose (sodium salt), methyl cellulose,hydroxyalkyl cellulose, and mixed ethers, such as methyl hydroxyethylcellulose, methyl hydroxypropyl cellulose, methyl carboxymethylcellulose and mixtures thereof, are preferably used, for example inquantities of 0.1 to 5% by weight, based on the detergent.

The detergents may contain derivatives of diaminostilbene disulfonicacid or alkali metal salts thereof as optical brighteners. Suitableoptical brighteners are, for example, salts of4,4′-bis-(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)-stilbene-2,2′-disulfonicacid or compounds of similar structure which contain a diethanolaminogroup, a methylamino group and anilino group or a 2-methoxyethylaminogroup instead of the morpholino group. Brighteners of the substituteddiphenyl styryl type, for example alkali metal salts of4,4′-bis-(2-sulfostyryl)-diphenyl,4,4′-bis-(4-chloro-3-sulfostyryl)-diphenyl or4-(4-chlorostyryl)-4′-(2-sulfostyryl)-diphenyl, may also be present.Mixtures of the brighteners mentioned may also be used.

Particularly where the detergents are used in washing machines, it canbe of advantage to add typical foam inhibitors to them. Suitable foaminhibitors are, for example, soaps of natural or synthetic origin whichhave a high percentage content of C₁₈₋₂₄ fatty acids. Suitablenon-surface-active foam inhibitors are, for example, organopolysiloxanesand mixtures thereof with microfine, optionally silanized, silica andalso paraffins, waxes, microcrystalline waxes and mixtures thereof withsilanized silica or bis-stearyl ethylenediamide. Mixtures of differentfoam inhibitors, for example mixtures of silicones, paraffins and waxes,may also be used with advantage. The foam inhibitors, more particularlysilicone- and/or paraffin-containing foam inhibitors, are preferablyfixed to a granular water-soluble or water-dispersible support. Mixturesof paraffins and bis-stearyl ethylenediamides are particularlypreferred.

The production of solid detergents according to the invention does notinvolve any difficulties and may be carried out in known manner, forexample by spray drying or granulation, the β-glucanase and otherenzymes, if any, and any other heat-sensitive ingredients, for examplebleaching agents, optionally being separately added at a later stage.Detergents according to the invention having a high bulk density, moreparticularly in the range from 650 g/l to 950 g/l, are preferablyproduced by the process comprising an extrusion step which is known fromEuropean patent EP 486 592. Another preferred method of production isgranulation as described in European patent EP 0 642 576. Liquid orpaste-form detergents according to the invention in the form ofsolutions containing typical solvents are generally produced simply bymixing the ingredients which may be introduced into an automatic mixereither as such or in the form of a solution.

EXAMPLES

To determine washing performance, cotton fabrics soiled withstandardized test soils were washed at 30° C. (detergent dose 80 g;water hardness 16°d; load 3.5 kg, short program) in a domestic washingmachine (Miele W 914 Novotronic®. The washing results (as the outcome ofdouble determinations) are shown in Table I below (in dE initial valueminus dE after washing, as measured with a Minolta® CR 310) for anenzyme-free detergent V1, for a detergent V2 with otherwise the samecomposition, but additionally containing 0.5% by weight of amylasegranules (Termamyl® 60T), for a detergent V3 which had the samecomposition as V2, but additionally contained 0.5% by weight of proteasegranules (activity 200,000 PU/g), for a detergent M1 according to theinvention which had the same composition as V1, but additionallycontained 0.125 U/g Cereflo®, for a detergent M2 which had the samecomposition as M1, but which instead of Cereflo® contained β-glucanasefrom Bacillus alkalophilus (DSM 9956) in a quantity producing the sameactivity, for a detergent M3 which had the same composition as V3 but,instead of Termamyl®, contained 0.125 U/g of Cereflo® and for adetergent M4 which had the same composition as M3 but, instead ofCereflo®, contained β-glucanase from Bacillus alkalophilus (DSM 9956) ina quantity producing the same activity.

TABLE Washing results (dE AW - dE) Washing result for soil Detergent A BC M1 45.1 32.0 42.5 M2 35.4 n.d. n.d. M3 48.3 33.4 50.5 M4 41.6 29.749.2 V1 31.8 26.7 41.1 V2 35.2 28.9 41.9 V3 35.7 30.3 49.7 Soil A: Oatflakes/cocoa B: Chocolate pudding C: Milk/cocoa n.d.: Not determined

It can be seen that detergents according to the invention aresignificantly superior in their cleaning performance to the comparisondetergents of directly comparable composition.

What is claimed is:
 1. A detergent composition comprising a β-glucanaseobtained from Bacillus alkalophilus (DSM 9956) wherein said compositionhas a glucanolytic activity of from 0.05 U/g to 1 U/g.
 2. The detergentcomposition of claim 1 having a glucanolytic activity of from 0.06 to0.25 U/g.
 3. The detergent composition of claim 1 further comprising atleast one protease.
 4. The detergent composition of claim 3 having aproteolytic activity of from 100 PU/g to 7500 PU/g.
 5. The detergentcomposition of claim 4 having a proteolytic activity of from 500 PU/g to5000 PU/g.
 6. The detergent composition of claim 1 wherein saiddetergent is free from amylase.
 7. The detergent composition of claim 1wherein said β-glucanase is absorbed onto supports or encapsulated inshell-forming substances.
 8. A process for removing polysaccharide soilson a textile comprising contacting said soils with a β-glucanaseobtained from Bacillus alkalophilus (DSM 9956) and having a glucanolyticactivity of from 0.05 U/g to 1 U/g.
 9. The process of claim 8 wherein anaqueous washing solution comprises said β-glucanase.
 10. The process ofclaim 9 wherein said aqueous washing solution has a glucanolyticactivity of from 0.2 U/l to 4 U/l.
 11. The process of claim 10 whereinsaid aqueous washing solution has a glucanolytic activity of from 0.25U/l to 1 U/l.